Process of condensing a 4-amino polyaryl methane and acetone



and discoloration and consequently Patented Sept. 9, 1952 ieqrnorationot, Delaware a a 610,172 CEEQ S 10. ?"obnnnnsmenaeammow 1 J c-rear; MET N m-aomrmm, impala, agate, w-Nitro, va ssg uer nnsantc.Qhemicai-.C0mmny;"St." 1 $;M9-*

' FNo Drawihs'. Application,July.2,, 193; i' serialiNo. 102,195,?

:Bhisihrehtioh :reiates itornew, .cQmnosi-tionsof matter.zMoreeparticuiarly it relates to rara kyh ated;1;2 dihydro.quino1ineS-.Iehas :beenttoundinaaccordance w t t ai w vention :that-a.1new--.endwnov.el zfemily :ofcomneuritis rpossessin auseful ,r pertisrmay e-E pared: by -.condensingan a a substituted aniline of th eneral:forml la y where A is representative-of ee-- more are- 'liphatic=ket0ne with matlc nuclei linked to the parapo'sition ofan anilinegnucleus through {an aligylene roup TheSfiillrimaryamine may; alsobecalled 4 -a nino nolyaryl-alkanes. w r v The new compounds have:excellent .oxidative inhibiting properties ,lfor organic-.ysubstanceswhich 1 tend: :to deteriorate idue to heat or. by absorption ofoxygenrfrom' thecair, as for example, rubber and alliedg'ums, unsaturatedvegetable oils, "essential oils, petroleum oils, and their derivativessuch as gasoline, soapsj aldehydes; synthetiogresins, and ithenlik, ineontrastto most xida ive l ahi ii jn 'w .matleri onta in nitr the newcom ounds. areifesistan ployed, as for example, in whit rubbervulcanizates Further, the new compounds are alsousefuljtor' improvingthe flexing properties. of rubh r n at s co a nin terho 'b ackg The new"compounds are readily pre ared 'by condensing, in the'presence ofasuitable catalyst; an aliphatic ketone containing. at"least'one methylgroup, such as acetone, methyl ethyl ketone, methyl-isopropyl ketone,methyl isobutyl ketone, and the like with a para aralkyl substitutedaniline-such'as the a amino diarylalkanes, the 4-amino-triarylalkanes,and the 4-aminotetraarylalkanes. As specific examples of these primaryamines are l-amino-diphenylmethane, 4 amino-'2'-methyl-diphenylmethane,-aminotriphenylmethane, -amino tetraphenylmethane, beta-(4-amino phenyl)ethylbenzene, alpha-(4- amino phenyl) :ethylbenzene, alpha-(d-aminophenyDpropylbenzene, alpha-(*l-amino phenyl) beta-,gamma-diphenylpropane, andthe like.

The chemical structure of the products obtained bycondensing analiphatic ketone withan arallcyl substituted aniline is not known butitis believed that the prdductsof--the reaction are a mixtureof=a-ralkylated-l ,2-dihydroquinolines of which the chief component is adaralky-l substituted 1,2-dihydroquinoline. However, the presentinvention is not limited to any assumption as to chemical structure butpertains broadly to the aralkylated 1,2-dihydroquinolines obtained by{reacting an aliphatic ketone-with an aralkyl substituted anilinewherein the primary amine group is in the 4-position with respect'to thearalkyl substituent.

staining -1 5 Claims, (01. 'ZGOE-BSI As exemplaryof the preparation ofthe new chemicals the following examples are i1lustra tiveand in'no wiseare to be construed as limitative thereof.

Example -1 Acetone vapors were passed into a suitable reaction .vesselequipped i with a thermometer,

stirrer, and reflux condenser, and containing 22.5 parts'rby Weight(substantiallly 0.12 mol)- of 4-amino diphenylmethane,

plus a small amount of a dehydrating catalyst at "1.2 -12.5";C .forover24 hours Uponrremova ofithere cesstacetone andiwaterlohcondensationbydistillat on; '28 .arts by wei ht (approximatelya;8 fi% yield) ".0. v toconsist principally ofzfiqbQIlZYkZQifirtfifilGthyl-l,Z-dihydroguinolinewas obtained,

The A-amin dinhenylmr ha ew em oyed in the above condensation ,wasobtained by simply reducing 4-nitr0 diphenylmethane. The latter chemicalwas prepared according to the procedure described in Berichte, vol. 29,p. 1303.

"Example 2 plus 0.2 part by weight of iodine at -125 C. fora period of127351101116. The. excess acetone andwater of condensation weredistilled-errand 27-:parts byeweight -:(approximately '93 yield) of aresinous product believed to "consist principally ofrd-diphenylmethyl-2,2l trimethyl-l 2- dihydroquinoline waswobtained;L-Ihe '4-amino triphenylmethane employed in the "above conat on waspreparedaccord ng to the pr cedure describedv in Annalenflzofi, .p. 1555'using benzhydrol and:- aniline hydrochloride as the.

starting materials and employing :anhydrous' zinc chloride as thecatalyst. V

In a similar manner 4-amino tetraphenylmethane,

condenses With-acetone to "produce an aralkylated 1,2 dihydroquinolinebelieved toconsist principally of "firt i hgn lmethyle2,2,4 trimeth,

yI-LZ-dIhydroquinoline. 4-amino tetra phenyl e ha e. mayprepared bycondensing trire i ous product believed a tire were compoundedcomprising.

, Industrial and Engi prepared according to the metl-idd escribedfBerichte, vol. 38, p. 1763, condo vtone to produce anaralkylated;,'l,,2f-dihyd ro quinoline believed to consistpi incipallyiof (at-methyl benzyl)-2,2,4-trimethyl-LZ-dihydrO- quinoline. .7 v. Asexemplary of the oxidative inhibiting prop erties of the new aralkylated1,2-dih'ydroquinolines the following hevea rubber 'zstocks suitable forthe tread portion of an automobile Parts by weight Smokedsheetsrubber;

Sulfur Morcaptobenzothiazole Aralkylated 1,2dihydroquinoline of E ample1 Aralkylated 1,2-dihydroquinoline of Example 2 m; rubber stocks'f socdmpounded" ere? tively'at 135 C." 'Testf strips wer'cutff ro'm thevulcanized stocks and artiflciallyaged for Shours at '135 C.- "in-"anairf bomb under 60 poundsper' square inch pressure. The table belowet'sforth e w heo ems atchels Original Tensile Retained After Aging 3hours at '1; Minutes The foregoing data {clearly show" that the 1various rubber stocks treated with aralkylated 1,2-dihydroquino1inespossess excellent ag'e' re-'" 55 sistant propertiesi These new compoundsalso exhibit good tanti-flx cracking "properties, as for example, thefollowing resultsw'ere' obtained-upon Q 'Percento'b flexing "the curedhvearubber StocksB and "CF above described, einpl'oying" a flexingmachine'as set forth by'L vi-ocopery Analytical Editiorffof 'e'eringoheistry, vcijfz no, eraser-3949" failure) Aged 72 hourslt lil0 l'in an air'cireu A Obviously, the iexamples 'se V firt Latte j j that rubberjcompositions: containing an,a',ralk y1 (kiloeycles to e'lg d-tlfidlhydroquinolinemm markedly resistant o he se toriciratin innoeiib s ori e i e', hea and oxidation. The new aralkylated 1,2-dihydroi? Jiquinolines are further characterized by their nondiscoloringproperties, that is they exhibit remarkable resistance to lightdeterioration. v While the above data describes only specific similaroxidative inhibiting properspe'cifi'c examples which are characterizedby the properties noted above are the respective condensation productsof alpha-(4- aminophenyl) ethylbenzene and beta-(4-amino plienyl)ethylbenzene with acetone.

While certain specific embodiments of this invehtidn havebeen describedin detail-"heriniit is to be" understood that the) invention'fis not soflimited for many odincatipnsmay be resorted" to such as varyi g theproportions of "the new chemicals, as for example "irom0.2' to 5" "partsby weight er parts rubber, employing other than natural" rubber-such asr11bber-substi-- tutes; synthetic rubber} and the like whether or notadmixed with fi1ler's",'"pig ments, accelerators,

.1. The; process; of preparing an and the like, without departing fromthe spirit or composition which v comprises heating. a.

C. under atmospheric pressure in the p esencefof,

a condensation catalyst acetone and polyaryl methane in 'whichjone"hydroger'ifof methane'is substituted by a 4-1ajn'iin6 phen'y'l group i1 and at least one other hydrogen is substituted by a monocyclic arylhydrocarbon groum anyi ire mainingvalences of the, methane carbon beingsatisfied :by ;hydrogen,- removing :excess, acetone",

and-water of condensation.

2, The Process" offpreparin waterof condensation. I 3. The process of'preparing.

C. underatmospheric pressure in the presence of a condensationcatalystacet'one and 4,-ammOP... triphenylmethane, removing {excessacetone and Water of condensation.

clainrl. v 5. The product claim 2. I

GP' product by the prbges gu claim 7;

:REFERENC'E'S CiITED- Q The following "references 1 areof record in'tlie' file of'this patent:

'- N ED T TEs eA I 2,530,774 Kehe r; V

' H FERE E Reddelien et al., Berichte, vol. 65., fill 1521,

Busch et al., Berichte,;vol.- 3 8,- p

0i thenew'i'amily, all members of said timeles ,an antioxidatcomposition which'com'prises heating at 1211 X C. under atmosphericpressurein the presence of a condensation catalyst acetone. and lij-aminorfi diphenylmethane, removing excess ,acetonewjand I I M an.composition which comprisesheatingat 1205125? prepared byjtheprocessof;-

' JLOSEPI-I RL-I GRAM'Q I 1 -F.'isoher,-Annalen, vol. 206; pp., l55-d (1880) I I

1. THE PROCESS OF PREPARING AN ANTIOXIDANT COMPOSITION WHICH COMPRISESHEATING AT 120-125* C. UNDER ATMOSPHERIC PRESSURE IN THE PRESENCE OF ACONDENSATION CATALYST ACETONE AND A 4-AMINO POLYARYL METHANE IN WHICHONE HYDROGEN OF METHANE IS SUBSTITUTED BY A 4-AMINO PHENYL GROUP AND ATLEAST ONE OTHER HYDROGEN IS SUBSTITUTED BY A MONOCYCLIC ARYL HYDROCARBONGROUP, ANY REMAINING VALENCES OF THE METHANE CARBON BEING SATISFIED BYHYDROGEN, REMOVING EXCESS ACETONE AND WATER OF CONDENSATION.